Oximino-containing polymers



United States Patent 3,261,817 OXIMINO-CON AINHNG POLYMERS Rudolph J.Angelo, Wilmington, Del., assignor to E. I. du Pont de Nemours andCompany, Wilmington, Del., a corporation of Delaware No Drawing. FiledDec. 12, 1962, Ser. No. 244,017 11 Claims. (Cl. 26080) This inventionrelates to novel polymeric compositions suitable for producing shapedarticles.

The invention resides in a polymer composition having a substantiallyhydrocarbon backbone or chain and having oxirnino groups either alone oras part of large radicals appended to carbon atoms in the chain.

Specifically, the invention is a substantially linear filmformingpolymer having the recurring unit:

Hz R l I l L X l wherein R is selected from the group consisting ofhydrogen and alkyl of 1 to 4 carbon atoms, preferably methyl and whereinX is the oximino-containing radical preferably selected from the groupconsisting of Y, -fiY and IIICY II II 0 wherein R being alkyl of l to 6carbon atoms and R being selected from the group consisting of hydrogen,aryl and alkyl of l to 6 carbon atoms.

The polymer may be a homopolymer or a 'copolymer with one or morecopolymerizable monomers where the oximino-containing unit, representsat least 1% by weight, preferably at least 50% ,by weight of thecopolymer. As monomers for copolymerization with the oXimino-containingmonomers any of the following may be used: methyl, ethyl, isobutyl,butyl, octyl and Z-ethyl-hexyl acrylates and methacrylates; phenylmethacrylate, cyclohexylmethacrylate, p cyclohexyl phenylmethacrylate,methoxyethyl methacrylate, chloroethyl methacrylate, 2- nitro-2-phenylpropyl methacrylate and the corresponding esters of acrylic acid; methylalpha-chloroacrylate, octyl alpha-chloroacrylate, methylisopropenylketone, acrylonitrile, methacrylonitrile, methyl vinyl ketone, vinylchloride, vinyl fluoride, vinylidene fluoride, vinylidene chloride,vinyl acetate, vinyl propionate, vinyl chloroacetate, vinyl bromide,styrene, vinyl naphthalene, ethyl vinyl ether, N-vinyl phthalimide,N-vinyl succinimide, N-vinyl carbazole, isopropenyl acetate, methylenediethyl malonate, acrylamide, methacrylamide or mono-alkyl substitutionproducts thereof, phenyl vinyl ketone, diethyl fumarate, diethylmaleate, methylene diethyl itaconate, dibutyl itaconate, vinyl pyridine,maleic anhydride, ethyl vinyl ether, 2-chloroethyl vinyl ether, divinylether, 2- hydroxy ethyl vinyl ether, allyl ethyl ether, 2-methylallylethyl ether, Z-methylallyl n-propyl ether, Z-methylallyl, 2-hydroxyethylether, di-(Z-methylallyl) ether, 2-chloroallyl ethyl ether,di-(allyloxymethyl) ether, Z-methylallyloxypropylene oxide, isopropylvinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexylvinyl ether, 2- rnethoxyethyl vinyl ether, n-propyl vinyl ether,sec-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether,isoamyl vinyl ether, n-hexyl vinyl ether, n-decyl vinyl ether,n-octadecyl vinyl ether, isoprene, 2-ethyl-l,3-butadiene,2-propyl-l,3-butadiene, 2-n-hexyl-l,3-butadiene, 2- cyclohexyl 1,3butadiene, 2-ethoxy 1,3 butadiene, 2-

3,261,817 Patented July 19, 1966 phenyl-1,3-butadiene,3-methyl-l,3-pentadiene, 3-methyl- 1,3-hexadiene,4-methyl-1,3-hexadiene, 3-ethyl-1,3-heptadiene,3,7-dimethyl-1,3-octadiene, 2-tolyl-l,3-butadiene,2-xylyl-l,3-butadiene, 1,3-butadiene, 3,4-diethyl-l,5-hexadiene,3-methyl-l,5-hexadiene, 3,4-dimethyl, 1,5-hexadiene,3,5-dimethyl-l,6-heptadiene, 4-phenyl-1,6-heptadiene and4-cyclohexyl-1,6-heptadiene.

The oxirnino monomer having the formula wherein R and X are as definedpreviously is prepared by reacting the oximino of a ketone or analdehyde, e.g. acetone oxime with the unsaturated compound e.g. acrylicester or halide, vinyl isocyanate, vinyl ether, or the like at atemperature below 20 C. in an organic medium. The organic liquid usedmay be any of the usual hydrocarbon solvents: pyridine, petroleum ether,benzene, etc. When forming the oximino monomer of a vinyl ether, acatalyst such as a mercuric acetate may be used and the method oftransetherification followed. This method is described by W. H. Watanabeand L. E. Conlon, Journal of American Chemical Society, 79, 2828 (1957).

In any case, the reaction is exothermic and an ice bath may be used toprevent undue rise in temperature. After reaction is substantiallycomplete, the resulting mixture is agitated and warmed to about roomtemperature. The oximino monomer may then be isolated by any of themethods known, e.g. crystallization, extraction, etc.

The oximino monomers that are operable in this invention include thosederived from the oximes of diethyl ketone, di-n-propyl ketone,diisopropyl ketone, di-n-butyl ketone, diisobutyl ketone, di-n-amylketone, diisoamyl ketone, di-n-hexyl ketone, di-n-heptyl ketone,di-n-octyl,

ketone, di-n-nonyl ketone, di-n-decyl ketone, di-n-undecyl ketone,di-n-dodecyl ketone, di-n-fridecyl ketone, di-npentadecyl ketone,di-n-heptadecyl ketone, methyl ethyl ketone, methyl n-propyl ketone,methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone,methyl sec.-butyl ketone, methyl tert.-butyl ketone, ethyl n-propylketone, ethyl isopropyl ketone, ethyl n-butyl ketone, methyl n-amylketone, methyl n-hexyl ketone, methyl nheptyl ketone, methyl n-octylketone, methyl n-nonyl ketone, methyl n-decyl ketone, ethyl n-amylketone, ethyl n-hexyl ketone, ethyl n-heptyl ketone, ethyl noctylketone, ethyl n-nonyl ketone, ethyl n-decyl ketone, methyl thienylketone as well as those from oximes of formaldehyde, acetaldehyde,propionaldehyde, n-butyraldehyde, isobutyraldehyde, n -valeraldehyde,isovaleraldehyde, pivalaldehyde, n-caproaldehyde, n-heptaldehyde,n-caprylaldehyde, n-pelargonaldehyde, n-caprinaldehyde,nundecylaldehyde, n-lauraldehyde, n-tridecanal, n-myristaldehyde,n-palmitaldehyde, n-stearaldehyde, acrolein, crotonaldehyde, aldol,furfural, benzaldehyde, l-naphthaldehyde, Z-anthraldehyde,thiophenaldehyde.

The process for preparing the homopolymers or copolymers involvessubjecting the oximino monomer alone or with at least onecopolymerizable monomer, preferably in a liquid hydrocarbon orhalogenated hydrocarbon solvent such as hexane, benzene, toluene,tetrachloroethylene, to a temperature of 40 to 300 C. and a pressure ofl3,000 atmospheres in the presence of a catalyst for a contact timesuflicient to form the copolymer, usually at least 20 seconds for acontinuous process and at least 3 minutes for a batch process, and thenisolating the resulting copolymer.

When high pressures are used, 800 atmospheres and above, a conventionalperoxide (di-tertiary-butyl peroxide) or azo catalyst(alpha,alpha'-azobisdicyclohexanecarbonitrile) may be used and thetemperature is preferd ably 175 C. The azo catalysts are preferred sincethey yield polymers that can be formed into films by pressing, meltextrusion in solvent coating.

It is believed that the essential feature of this type of catalyst, ormore properly termed initiator, is that they are capable of generatingfree radicals. These free radical initiators, whether they be generatedfrom a peroxide compound or from an azo-type compound combine with apolymerizable monomer to form a new free radical; the new free radicalcombines with another monomer molecule to form still another freeradical; this process is repeated until three is propagated a longpolymer chain, as is well known in the art. Polymer chain growthterminates when the free radical-bearing polymer fragment encountersanother free radical which, for example, may be another growing polymerchain or an initiatorfree radical.

Typical peroxides which release free radical to function as initiatorsinclude benzoyl peroxide, di-tertiary-butyl peroxide, di-tertiary-butylperoxydicarbonate, 2,2-bis-(tertiarybutylperoxy) butane, dimethyldioxide, diethyl dioxide, dipropyl dioxide, propyl ether dioxide andpropyl methyl dioxide. Orangic hydroperoxides also applicable are, forexample, tertiary-butylhydroperoxide, cumene hydroperoxide, ethylhydroperoxide, and can be used to initiate polymerizations of this kind.Combinations such as ammonium persulfate with a reducing agent can alsobe used. Typical azo compounds which decompose to liberate free radicalsfor initiation of polymerization include such catalysts asalpha,alpha-azobisdicyclohexanecarbonitrile,alpha,alpha'-azobisisobutyronitrile, triphenyl methylazobenzene, 1,1azodicycloheptanecarbonitrile, alpha,alpha'-azobisisobutyramide, lithiumazodisulfonates, magnesium azodisulfonate, dimethylalpha,alpha'-azodiisobutyrate, alpha,alpha-azobis( alpha,gamma-dimethylvaleronitrile) andalpha,alpha-azobis(alpha,beta-dimethylbutyronitrile) Coordinationcatalysts, as defined in US. Patent 2,822,357, may also be used toefiect copolymerization. Specifically, such coordination catalysts arecomposed of:

(A) A compound containing at least one metal of the group consisting ofmetals of Groups IVa, Va and VIa of the Periodic Table, iron, cobalt,copper, nickel and manganese, said metal having directly attachedthereto at least one substituent from the group consisting of halogen,oxygen, hydrocarbon and .O-hydrocarbon; and

(B) A reducing compound seleced from the group consisting of metalhydrides and compounds having a metal of Groups I, II and III of thePeriodic Table, said metal being above hydrogen in the electromotiveseries, attached directly through a single bond to a carbon atom, saidcarbon atom selected from the group consisting of trigonal carbon andtetrahedral carbon.

In the above definitions, Periodic Table means Mendeleeifs PeriodicTable of the Elements, 25th ed., Handbook of Chemistry and Physics,published by the Chemical Rubber Publishing Co. Specific examples ofcompound (A) included in the above definition are titaniumtetrachloride, titanium tetrafluoride, zirconium tetrachloride, niobiumpentachloride, vanadium tetrachloride, vanadyl trichloride, tantalumpentabromide, cerium trichloride, molybdenum pentachloride, tungstenhexachloride, cobaltic chloride, ferric bromide,tetra(2'ethylhexyl)-titanate, tetrapropyl titanate, titanium oleate,octylene glycol titanate, triethanolamine titanate, tetraethylzirconate, tetra(chloroethyl) zirconate and the like. Specific examplesof compound (B) in this definition are phenyl magnesium bromide, lithiumaluminum tetraalkyl, aluminum trialkyl dimethyl cadmium, diphenyl tinand the like.

The Friedel-Crafts type catalysts are especially useful for thepreparation of polyers from the vinyloxy acetone oximes. Operablecatalysts of this type include boron trifiuoride, aluminum trichloride,aluminum tribromide, stannic chloride, stannous chloride, ferricchloride, zinc chloride, silicon tetrachloride, as well as complexes ofboron trifluoride with dialkyl ethers and carboxylic acids.

Polymerization is preferably carried out in a solvent medium. Among thesolvents which have been found useful in the present invention arehydrocarbons and halogenated hydrocarbons: hexane, benzene, toluene,cyclohexane, bromobenzene, chlorobenzene, o-dichlorobenzene,tetrachloroethylene, dichloromethane and 1,1, 2,2-tetrachloroethane.Heterocyclic compounds such as tetrahydrofuran, thiophene and dioxanemay also be used. In some instances, polymerization may be effectedwithout a solvent or in an emulsion or slurry system.

The invention will be more clearly understood by referring to theexamples which follow, Example 1 representing the best mode contemplatedfor practicing the invention. It is understood that the examples,although illustrating specific embodiments of the present invention,should not be considered limitative of the invention.

Example 1 In a reaction flask fitted with stirrer and thermometer andwith an ice bath for cooling there was added 31.4 grams (0.3 mole) ofmethacrylyl chloride and 18.3 grams (0.25 mole) of acetone oxime Whilethe temperature was maintained at 5 C. To this there was added 40 gramsof pyridine with cooling. A vigorous reaction took place with theformation of tan-colored crystals. The mixture was stirred for 20minutes while warming to room temperature and was then poured ontocrushed ice containing 350 ml. of 3% hydrochloric acid. The resultingdispersion was separated into two layers, one an oil layer and the othera water layer. The oil was separated and the remaining water layer wasextracted four times with ethyl acetate. The oil and the extracts fromthe water layer were combined and dried over anhydrous calcium sulfate.The solvent was removed by distillation and the remaining liquid waspurified by vacuum distillation. There were obtained 25.5 grams (72% oftheoretical) of a clear, colorless liquid boiling at 9294 C. at 8-9 mm.11 1.4597. An infrared spectrum of the liquid showed strong absorptionbands at 6.05, 5.75 and 11.2-11.4 microns characteristic of C=N, C=O and-C=CH Analysis.-Calculated for C H O N: C, 59.55; H, 7.85; N, 9.92.Found: C, 59.48; H, 7.82; N, 8.65, 9.91.

The product was methacryloxyacetone oxime.

A small glass vial was evacuated, flushed with nitrogen and filled with6 grams of met-hacryloxyacetone oxime and 0.03 gram ofazobisisobutyronitrile. The vial was sealed and kept in a constanttemperature bath at 60 C. for two days. After about 15 hours the liquidhad almost completely solidfied and was slightly yellow. After two daysthe vial was broken and a light-yellow hard glassy rod of polymer wasobtained. The yield was quantitative.

The polymer was dissolved in dimethylacetamide, precipitated intoheptane and washed with heptane to give 4.47 grams of a light yellowcolored powder. The polymer had an inherent viscosity (0.5 gram in ml.of dimethylacetamide) of 0.59. The polymer was dissolved indimethylacetamide and cast on a glass plate to give a sparkling clearfilm. The films were stiff and self-supporting. An infrared spectrum ofthe film indicated the polymethacryloxyacetone oxime structure. The filmwas readily dyeable and had low static susceptibility.

Example 2 Acetone oxime (14.6 grams of 0.2 mole) Was dissolved in amixture of 200 ml. of petroleum ether and 50 ml. of benzene. Thesolution was cooled to 5 C. in an ice bath and 13.8 grams (0.2 mole) offreshly prepared vinyl isocyanate was added over a period of fiveminutes during which the temperature rose to 25 C. After the vinylisocyanate was added the ice bath was removed and the solution wasallowed to warm to room temperature. The solution became cloudy andfinally a clear oil separated. The oil was crystallized by cooling togive .a white solid. The solid was washed with cold petroleum ether andvacuum dried to yield 21.4 grams (75.5% of theoretical) of productmelting at 4445 C. Recrystallization of this solid product from ethylacetate/petroleum ether gave a white crystalline solid melting at 45-46C. An infrared spectrum absorption bands at 6.05 and 11.2-11.4 micronscharacteristic of the vinyl urethane of ace-tone oxime.

Analysis.-Calculated for C H N O C, 50.69; H, 7.09; N, 19.71. Found: C,50.97; H, 7.31; N, 19.67.

Following the polymerization procedure described in Example 1, the vinylurethane of acetone oXime (2.0 grams in 10 ml. of benzene with 0.01 gramof a20- bisisobutyronitrile) was polymerized at 75 C. for two days andgave a solid product which could be pressed into a still film whichcould be readily dyed and printed.

Example 3 The monomer was prepared by reaction of acetone oxime withvinyl n-butyl ether in the presence of mercuric acetate as catalystfollowing the method of transetheri-fication described by W. H. Watanabeand L. E. Conlon, J. Am. Chem. Soc. 79, 2828 (1957). Elementary analysisand infrared absorption confirmed the liquid product as vinyloxy acetoneoxime.

Vinyloxy acetone oXime was polymerized by the reaction of borontrifluoride catalyst. Boron trifluoride was bubbled into a solution offive grams of vinyloxy acetone oxime in 50 ml. of petroleum ether at 25C. at a rate of 10 ml./minute for 10 minutes. The solution was thenwarmed to 75 C. for six hours. The polymeric product was pressed at 125C. into a clear, stilf film. Inherent viscosity of the polymer was 0.48(0.1 g. in 100 ml. of dimethylacetamide at 30 C.).

Examples 4-16 Following the general procedure described in Example 1,the following homoand copolymerizations were carried out. The resultsare shown in tabular form in the table below.

What is claimed is: 1. A linear film-forming polymer having therecurring Ill'llt:

wherein R is selected from the group consisting of hydrogen and alkyl of1 to 4 carbon atoms; and

X is an oximino-containing radical selected from the group consisting ofY having the formula R being alkyl of 1 to 6 carbon atoms, and R beingselected from the group consisting of hydrogen, aryl and alkyl of 1 to 6carbon atoms.

of the polymer.

4. A polymer as in claim 1 wherein said oXimino-containing recurringunits represent at least 50% by weight of the polymer.

5. A self-supporting film of a polymer having the recurring unit:

wherein a' L I R is selected from the group consisting of hydrogen andalkyl of 1 to 4 carbon atoms; and

Example Monomer Initiator Temperature-Time Remarks 4 4.0 g. MAAO 0.05 g.Benzoyl Peroxide. 75 C.-5 hours Stilt films from solvent casting andmelt pressing,

inherent viscosity, 0.14. 5 0.9 g. MAAO, (1 ml. benzene) 0.02 g. Benzoinmethyl- 25 C.-24 hours Clear films from viscous solution, inherentviscosity,

ether, UV light. 0.16. 6 3.0 g. MAAO, 3.0 g. Ethyl 0.03 g. azo 65 C.-2days Clear flexible films, inherent viscosity 0.33. Nitro- Acrylate. genanalysis indicated mole percent combined ethyl acrylate. 7 1.5g. MAAO,1.5g. Styrene.-. 0.05 g. azo C.-5 days Product has 55 mole percentstyrene, clear films,

inherent visosity, 0.25. 8 3.0 g. MAAO 3.0 g. Acrylo- 0.03 g. azo C.-4days Clear, slightly yellow films. nitrile and ester absorpnitrile. tionshown in infrared, inherent viscosity, 0.42. 9 1.58 g. MAAO, 1.5 g.Vinyl 0.05 g. azo C.3 days Tacky polymer shows good adhesivecharacteristics.

ceta e. 10 4.0 g. VUAO, 2.0 g. Methyl 0.05 g. azo 00 C.-2 days Clearfilms, inherent viscosity, 0.35, good dye- Methacrylate. ability. 11 3.5g. VUAO, 2.5 g. Vinyl 0.04 g. azo 60 C.-2 days Clear, stiff films, gooddyeabi1ity.

Pyrollidone. 12 307g. urg ng), 2.0 g. Methyl 0.02 g. Benzoyl Peroxide...75 0.5 hours Flexible film, good adherability to inks and dyes.

my e one. 13 3.5 g. VOAO, 2.5 g. Styrene. 0.03 g. azo 65 C.-3 days Clearfilm, good dyeability. 14 2.5 g.VUAO, 1.5 g. Butadiene. 0.03 g. azo 60C.-2 days Clear, flexible film, good adherability to inks, low

static susceptibility. 15 1.0 g. MAAO, 5.0 g. Vinyl 0.02 g. AcetylBenzoyl 40 C.-18 hours Still film, low static susceptibility.

Chloride. Peroxide. 16 3.0 g. VUAO, 3.0 g. Vinyli- 0.03 Azo 40 C.-24hours Clear, tough film, low static susceptibility.

dene Fluoride.

Legend- Azo=Azobisisobutyronitrile.

=1.5 grams in 100 m1. of dimethyl tormamide at 30 0. =0.5 gram in 100ml. of dimethylacetamidc at 30 C =Treated with 3% aqueous solution ofMAAO =Methacryloxyacetone Oxime. VOAO =Vinyloxyacetone Oxime. VUAO=Vinyl Urethane of Acetone Oxime.

Latyl Red M.G. (E. I. du Pont de Nemours & 00.), 2 hrs. at

X is an oximino-containing radical selected from the group consisting ofY, (EY, and ITI(IY Y having the formula 1' 2 (I3=NO 3 R being alkyl of lto 6 carbon atoms, and

R being selected from the group consisting of hydrogen, aryl and alkylof l to 6 carbon atoms.

6. A linear film-forming copolymer of wherein R is selected from thegroup consisting of hydrogen and alkyl of l to 4 carbon atoms, and

X is an oximino-containing radical selected from the group consisting ofY, (|J--Y, and -NCY I H O Y having the formula R being alkyl of l to 6carbon atoms, and

R being selected from the group consisting of hydrogen, aryl and alkylof 1 to 6 carbon atoms, and an alkyl acrylate; said oximino-containingradicals being present in at least 1% by weight of said copolymer. 7. Alinear film-forming copolymer of R1 CHZ=(IJ 1% wherein R is selectedfrom the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms,and

X is an oximino-containing radical selected from the group consisting ofY, -$[7Y and --N-$ll'Y Y having the formula 1]: C=N-O R being alkyl of 1to 6 carbon atoms, and

R being selected from the group consisting of hydrogen, aryl and alkylof 1 to 6 carbon atoms; and acrylonitrile; said oxirnino-containing radicals being present in at least 1% by weight of said copolymer. 8. Alinear film-forming copolymer of R1 CH2=(IJ wherein R is selected fromthe group consisting of hydrogen and alkyl of l to 4 carbon atoms, and

X is an oxirnino-containing radical selected from the group consistingof Y, CY,

Y having the formula Y having the formula R2 (|3=NO- 1'2 R being alkylof l to 6 carbon atoms, and R being selected from the group consistingof hydrogen, aryl and alkyl of 1 to 6 carbon atoms in an inert organicsolvent to a temperature of 40 C. to 300 C. and a pressure of l to 3,000atmospheres in the presence of a free radical initiating catalyst for acontact time sufficient to polymerize said monomer; and thereafterisolating the resulting polymer. 10. A process as in claim 9 whereinsaid catalyst is alpha,alpha-azobisdicyclohexanec-arbonitrile.

11. A linear film-forming copolymer of lid CH2=C wherein R is selectedfrom the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms,and X is an oximino-containing radical selected from the groupconsisting of Y, -fi2-Y and -N]oY Y having the formula 1' 2 $=N-O a Rbeing alkyl of 1 to 6 carbon atoms, and R being selected from the groupconsisting of hydrogen, aryl and alkyl of 1 to 6 carbon atoms; and avinyl ester selected from the group consisting of vinyl acetate, vinylpropionate and vinyl chloroacetate; said oXimino-containing radicalsbeing present in at least 1% by weight of said copolymer.

(References on following page) 9 19 References (Iited by the ExaminerOTHER REFERENCES UNITED STATES PATENTS Walling: Free Radicals inSolution, John Wiley and Sons, Inc. (1957), page 513. 3037969 6/1962Hanllns et a1 260 r Donaruma: J. Org. Chem, vol. 26, pages 577-9 (1961).FOREIGN PATENTS JOSEPH L. SCHOFER, Primary Examiner. 1,054,619 4/1959 GeDONALD E. CZAJA, Examiner.

848,826 9/ 1960 Great Britain. H. WONG, Assistant Examiner.

1. A LINEAR FILM-FORMING POLYMER HAVING THE RECURRING UNIT: